Agglomerating activated carbon

ABSTRACT

Agglomerated activated carbon is prepared by treating activated carbon particles with a water-insoluble lignin binder. The binder is employed in amounts of from 2 to 25 percent by weight based on the carbon. The lignin binder and the carbon particles are mixed together with water to form pellets, then dried to form an agglomerated granular particle.

Dimitri et a1.

1 Aug. 26, 1975 1 AGGLOMERATING ACTIVATED CARBON [75] Inventors: Mitchell 5. Dimitri; Albert J. Repik,

both of Charleston, SC.

[73] Assignee: Westvaco Corporation, New York,

22 Filed: Nov. 18, 1971 211 App1.No.: 200,240

[52] US. Cl 252/428; 23/314; 260/124 R; 264/1 17 [51] Int. C1. B01J 21/18; C09C H58 [58] Field of Search 264/117, 29; 23/314; 252/444, 421, 428; 423/460; 260/124 R [56] References Cited UNITED STATES PATENTS 2,228,976 1/1941 Reboulet 260/124 R 2,648,637 8/1953 Rodman, Jr. 252/421 2,664,377 12/1953 Van Beckum 161/246 X 2.850403 9/1958 Day v 23/314 3,077,439 2/1963 Shea, Jr. et al.. 264/117 3,454,502 7/1969 Hi1tgen 252/444 X 3,533,961 10/1970 Voet et a] 23/314 3,544,507 12/1970 Lloyd 260/39 3,560,346 2/1971 Gunter... 264/117 3,592,779 7/1971 Kiikkam. 252/421 3,637,464 [/1972 Walsh 264/117 X 3,651,179 3/1972 Shea et a1. 264/117 3,697,497 10/1972 Falkehag 260/124 A 3,699,091 10/1972 Dimitri 260/124 R OTHER PUBLICATIONS Kirk-Othmer, Vol. 12, 1969, pp. 372-381. The Condensed Chemical Dictionary, 1966, pp. 58 and 556,

Primary Examiner-Robert F. White Assistant Examiner-Thomas P. Pavelko Attorney, Agent, or Firm-Richard L. Schmalz; Ernest B. Lipscomb, 111

[ 5 7 ABSTRACT Agglomerated activated carbon is prepared by treating activated carbon particles with a wateninsoluble lignin binder. The binder is employed in amounts of from 2 to 25 percent by weight based on the carbon. The lignin binder and the carbon particles are mixed together with water to form pellets, then dried to form an agglomerated granular particle.

6 Claims, No Drawings AGGLOMERATING ACTIVATED CARBON BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to agglomerating activated carbon particles. More particularly, this invention also relates to a method for coating activated carbon particles with a lignin binder to bond the carbon particles together and the activated carbon products made therefrom.

2. Prior Art Powdered activated carbon particles and dust from granular grades of activated carbon often present problems in handling. For instance, in mixing activated carbon with reclaimed rubber a large amount of dust is present. Ideally, the activated carbon for use with natural or synthetic rubber should be in the form of balls or pellets. It is also desirable agglomerate carbon particles for other uses, e.g., for filters, such as cigarette filters, air conditioning filters, heating plant filters, gas mask filters, and removal of hydrocarbons from gas streams, such as in automobiles.

Unfortunately, most binder systems do not satisfacto rily bond the activated carbon particles together and those binders which do have sufficient bonding properties seriously deteriorate the adsorptive capacity of the activated carbon. A number of binder systems have been set forth in which to varying degrees aid in preventing the dusting of carbon. Among these binders are those set forth in US. Pat. No. 3,544,507 to Lloyd and US, Pat. No. 3,352,788 to Conlisk.

It is the general object of the present invention to produce a treated activated carbon which substantially reduces dusting of the carbon particles without losing effectiveness. Another object of this invention is to bond activated carbon particles together without unduly impairing the surface area of the particles thereby inhibiting their adsorptive capacity. A further object of this invention is to provide a granulated activated carbon composition which is as effective an adsorbent as the powdered particles from which it was made.

Other objects. features and advantages of this invention will become apparent from the detailed description set forth below.

SUMMARY OF THE INVENTION lt has been found that activated carbon particles coated with a binder which comprises an alkaline digcstcd lignin in an aqueous solution are effective in bonding the activated carbon particles together and thereby prevent dusting. The lignin binders in solution are thoroughly mixed with the activated carbon particles and dried to substantially bond the particles together. The lignin binder is added in an amount of from 2 to 25?! by weight solids based on the carbon, preferably from ](J to by weight. The ammonium salt of lignin is preferred because upon subsequent heating after drying the salt may be broken down Modified lig nins may also be used. Those modified with hexamethylene tetramine are preferred because of their surface area. The coated, agglomerated particles greatly reduee the dusting of the smaller carbon particles, The bonded activated carbon may be made into sheets, cubes, rods, or other forms and can be employed as fil ters such as those of the types previously set forth, and in all other areas where activated carbon is conventionally employed. One further advantage of this invention is that the activated carbon treated in this manner is more easily wettable when hydrophylic lignins are used as binders; whereas, the untreated carbon heretofore required a surfactant to assist in wetting.

DETAILED DESCRIPTION OF THE INVENTION The activated carbons contemplated for use in this invention are activated carbons produced from any source which are in a powdered form, and carbon dust from granular grades that have been abraded. Particular powdered carbons to which this invention is applicable include such commercially available activated carbons as Pittsburgh types RB, RC, BL and Westvacos Nuchar, as well as other powdered activated carbons. Further, impregnated carbons can also be aided by this invention. The powdered and granular dusts usually have a mesh size below minus lOO mesh. Upon agglomeration the activated carbon pellets may vary, depending upon the amount of binder, water and mix ing but in any event the diameter can be controlled. The thus agglomerated activated carbon particles can then be crushed, if necessary, to the desired size, which typically varies for about 4 to 60 mesh.

The advantages of lignin as a bonding agent for fibrous material are well known. Lignin is itself the natural binding agent used by nature for cellulosic fibers, Obviously, such lignin as it occurs in nature must be substantially insoluble in water, else the wood would disintegrate. Similarly, lignin free acids, isolated from raw wood without substantial degradation, are also insoluble in waterv One of the main sources of lignin is the paper and pulp industry where lignocellulosic materials such as wood, straw, corn stalks, bagasse, and the like are processed to separate the cellulose or pulp from the lignin. The lignins that may be used in this invention are those obtained from the kraft and soda pulping processes, and are water insoluble, On the other hand lignins obtained from other pulping pro cesses, such as the sulfite process, are water-soluble when separated from the cellulose by dissolving in the spent liquor and are present in this liquor as a lignosulfonate. Because of their water solubility lignosulfonates are unacceptable for use in this invention.

The problem which presents itself in connection with the use of lignin as a binder for activated carbon particles is how to bring about intimate dispersion among the particles. It has been found that the alkali lignin may be intimately mixed with the small carbon particles by use of the aqueous solution of the ammonium salts of the lignin acids or hexamethylene tetramine modified alkali lignin. After mixing or pelletizing with at least percent water based on the total mixture, agglomeration occurs. The pellets are dried and the water of solution is evaporated, leaving the ammonium lig nate or hexamethylene-tetramine modified lignin bond ing the particles together. Upon further heating the am monium lignate decomposes into ammonia and the water-insoluble lignin free acid form, thereby providing an intimate product which is coalesced and bonded by means of the thermoplastic lignin in the free acid form.

In accordance with this invention, those lignins obtained from lignocellulosic material without substantial degradation, which forms water-soluble ammonium salts, may be mixed with the carbon particles, as the aqueous solution of lignin binder. The binder may then be decomposed, if desired, to the water-insoluble acid rorm by heat to produce agglomerated activated caraon particles. Because polyvalent metal salts of alkali ignin are water-insoluble, they provide no answer since )ecause of their insolubilty they do not coat the carbon and extruding may produce rods, sheets or other useful forms of an activated carbon having satisfactory strength and abrasion properties. The heating produces a coalesced thermoplastic binder which gives the de- :articles and because when heated to decomposition 5 sired properties. Pressure may also be used. Also the .hey leave an objectionable residue. dried agglomerated particles may be crushed to the size The solution of lignin binder is prepared by dissolving of conventionally used granular products and used for llkali lignin in a selected solvent which may be evapothe same purposes. The drying conditions are not criti- 'ated, leaving a lignin salt which will decompose upon cal limitations. for those skilled in the art will recognize ieating into a volative constituent and the lignin free that many combinations of temperature and/or pres- \Cld residue. It is generally desired to prepare solutions sure may be used to suit the particular binder and carif relatively high concentrations, more dilute solutions bon particle. nay be often taken advantage of, depending in part The invention is described in greater detail with the men the conditions of treatment, method of impregnaaid of the following examples. ion, and upon the amount oflignin required for the de- ;ree of bonding desired. For instance, especially suc- A E I iessfu] levels of binder Solids are in the range of l( A solution of ammonium lignate binder was prepared 25% sohds amofmt i bmder sohds by slurrying 4 pounds or precipitated ammonium salt of noted with the carbon particles is variable and may alkaline digested Iignin with 16 pounds of water and ange from 2 to y weight solids based carbon slowly adding 2.08 pounds of ammonium hydroxide. might. with 10m 25% being preferred The amount Of The solids content was 17%. This binder was added to as long as it is Within this range is not P activated carbon particles at various binder levels with y Critical aqueol-ls solution of ammonia is the water in a Hobart blender until pelletizing occurred. lreferred solvent, but quaternary ammonium com- 25 Th carbon particles prior to pelletizing were minds, such as the tmmlky] ammonium hydroxides pared to normal granular activated carbon and had the may also be employed. One such method for making f llowing hy ical properties:

Type Density Iodine Molasses Particle Size Analysis,% by weight Carbon lbs/Fl. Value Value +8M 8X30 60 50X I00 l00 200 200x325 325 Granular 10.8 89.3 60 1.2 42.6 42.5 10.1 5.1 Dust 93.5 157 0.07 0.10 L16 98.67

queous solutions of ammoniacal lignins is set forth in The formulations for carboin particle-binder mixtures LS. Pat. No. 3,1 17,] I5 to Webster. In addition to the are shown in the table below:

Percent Weight Wt. Ammonium Total Weight Total Percent Sample Binder Dust,g. Lignate Sol. Water Added Weight H20 H20 1 5 100 30.7 270 g. 295.4 73.3 2 10 100 64.6 250 g. 3043 73.8 3 20 100 145.5 180 g. 300.5 712 includes water in the binder mmonium lignate, an alkali lignin modified with hexiethylene tetramine may also serve as a binder. A iethod for making this modified lignin is set forth in LS. Pat. No. 3,697,497, to Falkehag, which issued ct. l0, I972. A modified lignin may be made accord- 1g to the Falkehag patent by reacting an alkaline soluon of alkali lignin with from 0. l7 to 2.0 moles of hexalethylene tetramine per mole of alkali lignin at a temerature between 70 and I80C. to form a water insolble modified lignin.

The carbon particles are thoroughly mixed with the gnin binder using any convenient mixing means as mg as thorough mixing is obtained. The mixture genally agglomerates best when there is present 70% of 1e total weight of the composition (mixture) as water. dditional water may be added to bring the mixture to 1e correct proportions. The mixing is continued until 1e particle agglomcrates to about l/l6 to A inch diam- ;cr spheres.

After agglomeration occurs, the water of solution is 'iven off, either by drying in air or by the aid of heat lch as in a forced air convection furnace. The dried 'oducts may then be used as is or subjected to further :ating and processing. For instance. further heating The carbon dust was found to pelletize quite well at water loading above Most of the pellets were in the [/16 to A inch diameter range. The total sample, larger than 30 mesh was estimated to be better than The level of ammonium lignate binder did not seem to efiect the pelletizing characteristics.

EXAMPLE 2 After pelletizing, the samples from Example 1 were dried in a forced air convection furnace. Each sample was crushed through an 8 mesh screen to get the material to the same relative particle size as granular activated carbon particles. The dried and crushed samples oflignin binder carbon particles were each heat treated at l,600F. under a nitrogen blanket for about 2 minutes in a 4' inch diameter rotary furnace to devolatize the binder.

To investigate the degree of abrasion that would result if the carbon particle-lignin binder samples were passed through a high temperature fluidized bed furnace, the heat treated material was fluidized in a 4 inch diameter column at about the same residence time and gas velocity found in the high temperature furnace. Prior to the fluid bed treatment each sample was screened to a nominal 8X30 mesh particle size distribu- What is claimed is: tion, and all 60 mesh fines were removed. Retention 1. Activated powdered carbon particles agglomertimes of S and 10 minutes were used. A sample of norated with a water-insoluble ammonium salt of alkali ligmal granular activated carbon was run for comparison. nin in an amount of 2 to 25% by weight based on the The gas velocity through the fluid bed was 0.96 ft./sec. 5 a b at a bed temperature of 70F. The results were: 2. Activated carbon particles according to claim 1 Percent Fines (-60 Mesh) Sample Retention time 5 minutes l minutes Normal granular 3 5 Dust at 5% hinder level 55 73 Dust at lOZ hinder level 22 36 Dust at 20% hinder level 6 9 At the 20% ammonium lignate binder levels the wherein said ammonium salt of lignin is present in an amount of fines (-60 M) was only twice that of normal amount of 10 to by weight of powdered carbon granular particles. particles.

3. Activated powdered carbon particles agglomer- EXAMPLE 3 ated with an alkali 1i nin obtained b reactin an alkag y 8 This example illustrates the efiect of surface area eline solution of alkali lignin with from 0.17 to 2.0 moles duetion of dedusted activated carbon particles coated f hex m thylene tetramine per mole oflignin at a tern H ligni" binder- TWO Samples of WESTVACO perature between 70C. and l80C., said lignin dried to CHAR l having a mesh Of 12 X 30 were added form products having large surface areas present in an at 5 Parts and P l P carbon of lignifl amount of from 2 to 25% by weight based on a powbinder. The procedure was as follows: 75 grams of the dered Carbon activated carbon particles were mixed in a Hobart N2 4 Activated carbon particles according to claim 3 blbndcl' with u Solution Of hexamethylene tetramif'le wherein said alkali lignin is present in an amount of i0 modified lignin. 42 grams at 17.8% solids. After 5 mmto 20% b weight of said powdered carbon. utes of mixing. I00 grams of water were added and the 5 A method f pmducing activated Carbon particles mixing continued until small spheres of agglomerated Which comprises; Curhn" were fmmed- Thc wet mass was dned m a a. adding powdered activated carbon particles to forced air convection oven at 230F. for 4 hours. The water containing from 2 m 25% by weight of said surface area of each sample was determined by the powdered Carbon Ofth3 ammonium sah Ofan alkali BET method and compared to a control sample. "gm", Said Water being at least 70% by weight based on said lignin and said carbon together, b. intimately mixing said powdered carbon particles, Sump, S f Am Mygm, ammonium salt of alkali lignin and water to coat each powdered carbon particle with said ammo Control 4O Agglomcratcd Dust :it In parts hinder c. continuing said mixing until said powdered carbon loading 48H particles form agglomerates of about 1/16 to A inch diameter spheres, and d. evaporating the water from said agglomerates at a These results indicate that a hexamethylene tetratemperature b l the decomposition temperature mine modified lignin binder acts efiectively as a binder f id ammonium salt f alkali |i i at 5 and 10 parts hinder per [00 parts of carbon parti- 6 Th h d f l i 5 which further comprises, clcs loading levels with decreases in surface area of heating said agglomerams from Which the water y and 549% rsspecnvcly- 50 has been evaporated in step (d) above the decom- ShOUld bf: understood, hOWeVfil' that the detailed position temperature of aid ammonium alt 0f 3]. description and specific examples set forth hereinabove kali li i thereby to decempose the ammonium while indicating preferred embodiments of this invensalt f alka i i ammonia and a f i tion are given by way of illustration only, since various kali gnin bound Carbon agglomerateq and g and modificalions W'thm the Spirit and Scope f. separating said ammonia from said free acid alkali of the invention will become readily apparent to those hghin bound agglomerateskilled in the art. k 1k UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,901 823 DATED August 26, 1975 |NVENTOR(S) Mitchell S. Dimitri and Albert J. Repik It is certified that error appears in the above-identifled patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 18, after the word "desirable" insert -to-.

Column 4, line 19, "or" should read --of-.

Column 4, line 31, in the first table heading, "SOXlOO" should read --60xlOO--.

Signed and Bcalcd this ninth D3) of December 1975 is; AL]

A ttest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner nj'latenrs and Trademarks 

1. ACTIVATED POWDERED CARBON PARTICLES AGGLOMERATED WITH A WATER-INSOLUBLE AMMONIUM SALT OF ALKALI LIGNIN IN AN AMOUNT OF 2 TO 25% BY WEIGHT BASED ON THE CARBON.
 2. Activated carbon particles according to claim 1 wherein said ammonium salt of lignin is present in an amount of 10 to 20% by weight of powdered carbon particles.
 3. Activated powdered carbon particles agglomerated with an alkali lignin obtained by reacting an alkaline solution of alkali lignin with from 0.17 to 2.0 moles of hexamethylene tetramine per mole of lignin at a temperature between 70*C. and 180*C., said lignin dried to form products having large surface areas present in an amount of from 2 to 25% by weight based on a powdered carbon.
 4. Activated carbon particles according to claim 3 wherein said alkali lignin is present in an amount of 10 to 20% by weight of said powdered carbon.
 5. A METHOD OF PRODUCING ACTIVATED CARBON PARTICLES WHICH COMPRISES: A. ADDING POWDERED ACTIVATED CARBON PARTICLES TO WATER CONTAINING FROM 2 TO 25% BY WEIGHT OF SAID POWDERED CARBON OF THE AMMONIUM SALT OF AN ALKALI LIGNIN, SAID WATER BEING AT LEAST 70% BY WEIGHT BASED ON SAID LIGNIN AND SAID CARBON TOGETHER, B. INTIMATELY MIXING SAID POWDERED CARBON PARTICLES, AMMONIUM SALT OF ALKALI LIGNIN AND WATER TO COAT EACH POWDERED CARBON PARTICLE WITH SAID AMMONIUM SALT OF ALKALI LIGNIN, C. CONTINUING SAID MIXING UNTIL SAID POWDERED CARBON PARTICLES FORM AGGLOMERATES OF ABOUT 1/6 TO 1/4 INCH DIAMETER SPHERES, AND D. EVAPORATING THE WATER FROM SAID AGGLOMERATES AT A TEMPERATURE BELOW THE DECOMPOSITION TEMPERATURE OF SAID AMMONIUM SALT OF ALKALI LIGNIN.
 6. The method of claim 5 which further comprises, e. heating said agglomerates from which the water has been evaporated in step (d) above the decomposition temperature of said ammonium salt of alkali lignin thereby to decompose the ammonium salt of alkali lignin into ammonia and a free acid alkali lignin bound carbon agglomerate, and f. separating said ammonia from said free acid alkali lignin bound agglomerate. 